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4.11 The Production of Other Novel Alginate Fibers 73
Table 4.11 Silver concentrations in contact solutions.
Duration of contact
Silver concentration in
contact solution (ppm)
Normal saline Human serum
30 minutes 0.50 2.18
48 hours 0.40 2.74
7days 1.32 3.74
Pseudomonas aeruginosa
0.01
0.1
1
10
100
1000
10 000
100 000
020406080
Time (hours)
Log percentage recovery
Sorbsan
Urgo sor b
Aquacel
Alginate+Ag
Figure 4.9 The antimicrobial action of silver-containing alginate fibers against
Pseudomonas aeruginosa. Adapted with permission from Qin [43].
surface of the bers can also be detached from the bers and get into the wound
exudate.
Table 4.11 shows the silver ion concentration when alginate ber containing 1%
AlphaSan RC5000 isplaced in contact with normalsaline or human serum. Itcan be
seen that the silver ions are slowly released into the solution, acting as an antimicro-
bial agent. More silver ions can be seen released into human serum, suggesting the
high silver binding abilities of the protein components in the wound exudates [43].
Figure 4.9 shows the antimicrobial action of silver-containing alginate bers
against Pseudomonas aeruginosa. There was 100% reduction in bacteria count
within ve hours when the bers were placed in contact with solutions containing
the bacteria. Under similar test conditions, the silver-containing alginate bers had
a far better antimicrobial eect than other common types of alginate bers [43].
4.11 The Production of Other Novel Alginate Fibers
From a wet-spinning point of view, the production process for alginate bers is one
of the cleanest processes used for man-made bers. The dissolution of sodium algi-
nate takes place in pure water and at neutral pH, while coagulation can take place
in a dilute aqueous CaCl
2
solution, again at a neutral pH and under room temper-
ature. This makes it easy for alginate to be used as a carrier for biologically active
74 4 The Production of Fibers From Alginate
compounds that can be added to the bers and still maintain their bioactivities in
the nished bers.
Fan et al. [16] prepared bers from alginate and gelatin blends by spinning their
solution through a viscose-type spinneret into a coagulation bath containing aque-
ous CaCl
2
and ethanol. The highest tensile strength was obtained when the gelatin
content was 30 wt% of the overall solid content. The water-retention values of the
blend bers increase with the increase in gelatin contents. There was strong inter-
action and good miscibility between alginate and gelatin molecules, as a result of
intermolecular hydrogen bonds.
Wang et al. [62] prepared bers from blends of alginate and soy protein by spin-
ning their solution through a viscose-type spinneret into a novel coagulation bath
containing aqueous CaCl
2
, HCl, and ethanol. Fibers with 10% soy protein isolate
had a tensile strength of 14.1 cN/tex in the dry state and 3.46 cN/tex in the wet state,
respectively, with elongation at break of 20.71% and 56.7%, respectively.
Kobayashi et al. [31] used alginate bers for enzyme immobilization. They spun
an aqueous mixture of sodium alginate and enzymes into divalent metallic ion
solution as a coagulation bath to produce enzyme-containing bers. The entrap-
ment yields of enzymes, such as glucoamylase, cyclodextrin glucanotransferase,
endo-polygalacturonase, and protease, were higher in the calcium alginate bers
than those found in calcium alginate beads made under similar conditions. It was
found that the yields increased with the increase in the extrusion rate through
the spinning nozzle because at a higher extrusion rate, the polymeric molecules are
more highly oriented along the ber axis, which can help prevent leakage of the
entrapped enzymes.
Polymer blending is a useful tool for the functional modication of alginate
bers and the resultant properties can be tailored for their applications in wound
dressings, cosmetic products, baby diapers, adult incontinence products, feminine
hygiene products, and other functional medical and hygiene materials where
specic functional performances are required. As been pointed out previously,
the blending of alginate with carboxymethyl cellulose is proven highly eec-
tive in enhancing the gelling properties of alginate bers whilst the addition of
silver-containing particles into alginate bers produces silver-containing alginate
bers with strong antimicrobial properties. In recent years, there have been many
attempts to combine alginate with chitosan through many dierent techniques
in order to generate bers that have the high absorbency of alginate bers and
strong antimicrobial performance of chitosan, thus possessing two key properties
important for medical and healthcare products.
Watersoluble derivativesof chitosan such as carboxymethyl chitosan and hydrox-
ypropyl chitosan can be mixed with aqueous sodium alginate solution to prepare
a homogeneous spinning solution which can be spun into a polyblend ber con-
taining both alginate and chitosan. Fan et al. [18] were able to prepare bers that
contain 10–70% carboxymethyl chitosan with antimicrobial properties. When the
carboxymethyl chitosan content was 30%, the tensile strength of the polyblend ber
was 13.8 cN/tex [17]. Jiang et al. [28] showed that the addition of carboxymethyl chi-
tosan can signicantly increase the absorption properties of alginate bers. Hu et al.
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4.11 The Production of Other Novel Alginate Fibers 75
[26] and Chang et al. [14] used co-electrospinning technique to combine alginate
and chitosan in the same polyblend ber.
Qin [47] developed a novel process whereby alginate and chitosan can be uni-
formly dispersed in the same spinning solution. In this process, an acid-resistant
derivative of alginate, propylene glycol alginate (PGA), was rst dissolved in water
and then mixed with an acidic chitosan solution. PGA is an esteried derivative of
alginate with excellent emulsifying properties, which is esteried with propylene
oxide at 70
∘
C under pressure with alkali as catalyst [37, 57]. Figure 4.10 shows a
schematic illustration of theconversionof alginic acid intopropyleneglycol alginate.
Because the carboxylic acid groupis esteried by propylene glycol to yield an ester
group, PGA is soluble in water while remaining stable in acidic environment upto
pH 3–4, when sodiumalginate would precipitate out as alginic acid. This toleranceto
acidic environment together with its strong salt resistance makes PGA highly valu-
able in foodstus and beverages with strong acidity and high levels of metallic ions
such as calcium and sodium, where PGA is able to improve the stability of acid in
foodstu and also prevent the lay down created by calcium and other high valued
metallic ions. In thespinning of the mixedsolution of PGA and chitosan,upon extru-
sion into an alkaline coagulation bath, chitosan precipitates out to form laments
that contain PGA, and during the subsequent processing, part of the ester groups in
PGA are hydrolyzed to generatecarboxylic acid groups that can hold a large amount
of water, with some ester groups reacting with the amine groups in chitosan to form
a cross-linked structure that helps to maintain a stable ber structure.
OH
OH
H
H
H
H
H
H
H
H
HH
H
H
H
H
H
H
H
H
4
1
1
1
4
4
4
1
GG
MM
H
H
O
O
O
O
O
O
–
O
–
O
–
O
–
O
O
O
–
O
O
O
O
OH
OH
OH
OH
O
OH
OH
HO
HO
α
β
β
α
OH
O
O
O
O
O
OH
O
O
O
–
O
–
HO
HO
OH
O
O
O
O
O
OH
H
H
H
H
H
H
H
H
HH
H
H
H
H
H
H
H
H
4
1
1
1
4
4
4
1
GG
MM
H
H
O
O
O
α
β
β
α
CH
2
CH
3
CH
CH
2
CH
3
CH
CH
2
CH
3
CH
CH
2
CH
3
CH
O
OH
OH
CH
2
CH
3
CH
OH
OH
Figure 4.10 Schematic illustration of the conversion of alginic acid into propylene glycol
alginate.
76 4 The Production of Fibers From Alginate
Table 4.12 Gel swelling ratio of propylene glycol alginate/chitosan
polyblend fibers.
Ratio between PGA and chitosan (g/g) Gel swelling ratio (g/g)
In de-ionized water In saline
0 : 100 2.91 2.88
5 : 100 3.45 3.10
10 : 100 4.57 4.15
20 : 100 5.78 4.65
30 : 100 7.65 5.22
Table 4.12 shows the gel swelling ratio of propylene glycol alginate/chitosan
polyblend bers made with dierent proportions of these two polymers. It can be
seen that the gel swelling ratio increases with the increased use of propylene glycol
alginate.
4.12 Historical Development of Alginate Fibers
Since the rst attempt to produce bers from alginate, there have been many appli-
cations of these bers. In the early stages of development, alginate bers were used
principally in the productionof water-soluble yarns that would dissolvein a scouring
process. These yarns were used as a support during the manufacture of ne lace, or
as draw threads in the production of hosiery. Fabrics from alginate bers were once
produced commercially for their re-resistant property, because of the high content
of metal ions in the ber [12, 13]. Alginate bers were also used for the manufacture
of bags used for the transportation of soiled hospital linen that was designed to dis-
solve in the wash. However, by the 1970s, they were replaced for these applications
by cheaper synthetic bers.
The rst person in modern times to recognize the potential valueof alginate bers
in surgery and wound management was George Blaine, a major in the Royal Army
Medical Corps. He showed them to be absorbable in tissue, sterilizable by heat, and
compatible with penicillin [8]. He also described how he had used alginate lms
clotted in situ for the treatment of wounds and burns in troop ship hospitals in the
Far East and described the use of alginate, sometimes in combination with plasma
as an alginate-plasma lm, as “puncture patches” over septal defects.
During a subsequent assessment of the use of alginate as hemostats and wound
dressings, Blaine reported their apparent lack of toxicity following a series of
animal studies in which bers were implanted into animal tissues, and gels made
from alginate were used to treat experimentally produced burns [9]. Successful
use of alginate-derived materials in aural surgery and neurosurgery was reported
by Oliver and Blaine [38]. Bray et al. [11] described the results of a three-month
trial into the use of alginate in the casualty department of Croydon Hospital where
alginates in the form of lms, wool, gauzes, and clots formed in situ by mixing
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4.12 Historical Development of Alginate Fibers 77
sterile solutions of calcium chloride and sodium alginate, were applied to a wide
range of wounds, including burns, lacerations, ulcers, and amputations. In all cases,
healing was rapid and uneventful. By the late 1940s and early 1950s, alginates were
being used in some 70 hospitals in the UK over a range of surgical specialties [10].
The revival of alginate bers began with a new theory in wound management.
Although it has a long history, the standard practice in wound management
remained fairly static until Winter published his work in 1962 on acute supercial
wounds in the domestic pig [43, 50], which showed that wounds covered with a
lm dressing maintained a moist environment and healed faster than those left to
dry out, heralding the advent of modern wound dressings based on the principle
of moist healing [46, 47]. In the early 1980s, as wound dressings based on the
moist healing principle were expanding, alginate bers and nonwoven fabrics
were found to have unique gel-forming characteristics whereby on contact with
wound exudates, sodium ions in the exudates can exchange with calcium ions in
the bers, and as the ion-exchange process proceeds, the bers absorb more and
more water to form a brous gel. For the alginate wound dressings, as water enters
the ber structure, the entire textile structure is transformed into a sheet of moist
gel, thus providing an ideal moist healing environment for the underlining wound.
Many clinical trials have shown that alginate wound dressings not only have the
high absorption capacities but also possess the ability to promote wound healing.
In order to further improve its clinical ecacy, many attempts have been made
to improve the alginate bers and wound dressings. Table 4.13 summarized ve
generations of alginate bers for the production of wound dressings.
Table 4.13 A summary of five generations of alginate fibers for the production of wound
dressings.
Stage Product Product characteristics Main brand
1G Calcium alginate ber Gelling bers made from high M
calcium alginate bers [63]
Sorbsan
TM
2G Calcium sodium
alginate ber
High absorption bers made
from high G calcium sodium
alginate bers [48]
Kaltostat
TM
3G Alginate/CMC
polyblend ber
Highly absorbent and
gel-forming bers made from a
mixture of alginate and sodium
carboxymethyl cellulose [45]
UrgoSorb
TM
4G Silver-containing
alginate ber
Antimicrobial alginate bers and
wound dressings containing
silver [41, 52]
UrgoSorb Silver
TM
5G Alginate and chitosan
polyblend ber
Highly absorbent and
antimicrobial bers and wound
dressings that combine the
unique properties of alginate and
chitosan [44, 49, 58]
GellinS
TM
78 4 The Production of Fibers From Alginate
4.13 Summary
Alginate is a natural polysaccharide with abundant supply in nature. By processing
alginate into bers, it is possible to obtain novel biomaterials that can be processed
further into woven, knitted, nonwoven, and many other forms of composite struc-
tures. Because it is a polymeric acid, alginate bers can be used as a carrier to deliver
zinc, silver, and other bioactive metal ions for wound care and other novel applica-
tions. In addition, since it is processed in an aqueous solution and in an aqueous
coagulation bath at a neutral pH, many bioactive materials such as enzymes can be
combined into the alginate bers to produce enhanced bioactivities.
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